DE102006005799A1 - Process for preventing or reducing aluminum silicate deposits in industrial processes - Google Patents

Abstract

Materials and a method are provided wherein polymers having at least 0.5 mole% of a side group or end group containing the group -Si (OR ") ¶3¶ (wherein R" is H, an alkyl group, Na, K or NH 4) may be used to control aluminum silicate deposits in an industrial process with an alkaline process stream, such as a kraft pulp mill process stream. When materials of the present invention are added to the alkaline process stream, they reduce and even prevent the formation of aluminum silicate deposits on surfaces of the equipment, such as evaporator walls and heating surfaces. The materials of this invention are effective at treatment levels which make them economical in practice.

Description

Summary the invention

The This invention describes materials and methods for the formation of Deposits on or in equipment used in industrial processes with alkaline process streams be used to prevent or inhibit.

background the invention

The Problem of deposits in and on process equipment, which used in industrial processes, and in particular in those with an alkaline process stream, is very well known. The Deposits are a significant problem when they do on the surface of process equipment, and they cause a loss in the heat transfer coefficient. Thus, these processes may require evaporator equipment additional To provide heat, which leads to higher costs leads.

An example of such an industrial process with an alkaline process stream is the kraft recovery process for papermaking, which has been known for over 100 years and is described in detail in many texts on the subject (see GA Smook, "Handbook for Pulp and Paper Technologists", 3 Edition). More recently, the development of closed cycles in Kraft mills has led to an increase in deposition problems in process equipment due to the build-up of aluminum and silicon in the system as described by PN Wannamaker and WJ Frederick in "Application of Solubility Data to Predict the Accumulation of Aluminum and Silicon" alkaline pulp mills ", Minimum Effluent Mills Symposium, 1996, page 303. It has therefore been a well recognized need to provide a method and compositions for inhibiting the formation of aluminum silicate deposits in kraft pulp mills. US 5,409,571 describes the use of terpolymers of maleic acid, acrylic acid and hypophosphorous acid as an inhibitor of deposits in kraft pulp mills. This type of polymer has been shown to be effective against calcium carbonate deposits, but has not been shown to be effective against aluminum silicate deposits.

Attachments for high grade High Level Nuclear Waste (HLNW) processes heavily radioactive solid and liquid scraps to minimize the volume of waste and the hazardous material for long-term storage to immobilize. HLNW treatment is currently performed via two procedures; one Procedure is carried out under acidic conditions and one under alkaline Conditions. Under alkaline process conditions is growth Of sodium aluminosilicate deposits a significant problem while the pre-treatment stage, before the vitrification of the waste.

In the pretreatment plant, the waste is evaporated, filtered, ion-exchanged and evaporated further. During evaporation can become Aluminum silicate deposits on the surfaces of evaporator walls and the heating surfaces form. Furthermore you can due to the structure of these deposits and precipitates also transfer lines be clogged, which requires a shutdown for maintenance.

The pretreated HLNW waste go to vitrification plants. HLNW waste goes into a melt preparation container, in which Silica and other glass-forming materials are added. The Mixture is then heated and the molten mixture is thereafter in size stainless steel containers poured, cooled and transported to a temporary storage, until a place for final disposal selected becomes.

From the operation of the vitrification unit, a portion of the Si-containing glass-forming materials are fed back to the evaporator unit (for pretreatment). The dissolved aluminum in the form of sodium aluminate and sodium silicate species slowly react in solution to form complex hydrated sodium aluminum silicate species. These species include families of amorphous aluminum silicates (aluminum silicate hydrogels), zeolites, sodalites, and cancrinites, collectively known as "sodium aluminum silicate." These nuclear waste streams also contain high concentrations of nitrate and nitrite ions (up to 2 M for each ion) and very high concentrations of OH ^- ions (up to 16 M in some areas of the tank). These factors greatly increase the rate of formation of aluminum silicate deposits. As a result, formed aluminum silicate deposits have a low solubility in the alkaline HLNW Leach.

by virtue of the incorporation of radioactive lanthanides and actinides into the cage structures the aluminum silicates and the coprecipitation of sodium diuranates Sodium aluminum silicate deposits are also considered an undesirable HLNW product viewed (Peterson, R.A. and Pierce, R.A., (2000), Sodium diuranate and sodium aluminosilicate precipitation testing results, WSRC-TR-2000-00156, Westinghouse Savannah River Company, Aiken, SC). It is therefore desirable for HLNW plants, including the volume of HLNW those which result from aluminum silicate deposits. It can thus be seen that the growth of sodium aluminosilicate deposits a significant negative economic and operational Has an influence on the treatment of nuclear waste.

It would be therefore desirable, a solution for the Problem with the sodium aluminosilicate deposits in the evaporation equipment for nuclear To provide waste.

Tries, to solve the above-mentioned problems have been limited success, see Wilmarth and coworkers (Wilmarth, W.R., Mills, J.T. Dukes, V.H., (2005), Removal of silicon from high-level waste streams via ferric flocculation, Separation Sci. Technol. 40, 1-11). These Authors have recommended the use of ferric nitrate for removal from Si from solution in the form of an iron (III) precipitate investigated to reduce the formation of aluminum silicate deposits or eliminate. Although this approach has certain merits, the disposal of high-grade iron (III) precipitate remains, and operation of an additional Filtration unit is required. W. R. Wilmarth and J. T. Mills, "Results of Aluminosilicates Inhibitor Testing ", WSRC-TR-2001-00230, also have the use of connections with low molecular weight inhibitors of deposits HLNW suggested but found none satisfactory would have been.

It There is therefore a need for an economical and effective process to build up To reduce aluminum silicate deposits on equipment which be used in industrial processes in which such Construction is a problem, such as in kraft pulp paper process and in the treatment of currents nuclear waste.

SUMMARY THE INVENTION

The present invention solves the above problems and others by providing materials and a process wherein polymers having at least 0.5 mol% of the group -Si (OR '') ₃ (wherein R '' is H, an alkyl group, Na, K or NH ₄ ) as an end group or side group can be used to reduce or eliminate aluminum silicate deposits in a process with an alkaline process stream, such as in a kraft pulp mill or in the treatment stream of a high-grade nuclear waste evaporation process. When materials of the present invention are added to these industrial process streams, they reduce and even prevent the formation of aluminum silicate deposits on the surfaces of the equipment. Moreover, the materials of this invention are effective at treatment levels which make them economical in practice.

DETAILED DESCRIPTION OF THE INVENTION

The The present invention is directed to a method and materials directed to the formation of aluminum silicate-containing deposits in an industrial process with an alkaline process stream, such as in process streams a kraft pulp mill or a stream in the treatment of high level nuclear waste, to diminish. The process stream to be treated may be any process stream which is alkaline and in which deposits occur, e.g. Black liquor, green liquor and white liquor of the Force process or a process stream in the evaporation of high-level nuclear waste.

The method comprises the step of adding to the process stream in an amount inhibiting aluminum silicate-containing deposits, a polymer having at least 0.5 mol% of side groups or end groups thereon containing -Si (OR ") ₃ , where R ''= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ . The amount of -Si (OR ") ₃ functionality present in the polymer is a sufficient amount to obtain the desired results and may range from as low as 0.5 mole% of the total monomer groups present in the polymer up to 100 mole -% lie. However, it will be most economical to use the least amount necessary to achieve the desired results. The polymers are preferred initially prepared as the silyl ether derivatives polymer Si (OR '') ₃ , wherein R '' = C ₁ -C ₃ alkyl, aryl, eg polymer Si (OCH ₂ CH ₃ ) ₃ or polymer Si (OCH ₃ ) ₃ , The Silyletherderivate can be added directly to the industrial process stream, or they may be prior to addition to the process stream hydrolyzed to the Silanolderivaten be, with polymers of the following generic structures are formed, Polymer-Si (OH _{3) 3,} Polymer-Si (ONa) ₃ , Polymer-Si (OK) ₃ and Polymer-Si (ONH ₄ ) ₃ . It is a favorable feature of this invention that any of these forms can be added to the process stream. The molecular weight of the polymer should be at least about 500, most preferably at least about 1000.

In a preferred embodiment, the group containing -Si (OR ") contains ₃ , wherein R" = H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ , a group according to -GRX-R '-Si (OR'') ₃ , where G = no group, NH, NR''orO; R = no group, C = O, O, C ₁ -C ₁₀ -alkyl or aryl; X = no group, NR, O, NH, amide, urethane or urea; R '= no group, O, C ₁ -C ₁₀ -alkyl or aryl; and R "= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ .

In one embodiment, the group is -NH-RX-R'-Si (OR ") ₃ , wherein R = no group, O, C ₁ -C ₁₀ alkyl or aryl; X = O, NH, an amide, urethane or urea; R '= no group, O, C ₁ -C ₁₀ -alkyl or aryl; and R "= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ .

worin x = 0,1-100%, y = 99,9-0%, und R = keine Gruppe, C₁-C₁₀-Alkyl, Aryl oder -COX-R'-, worin X = O oder NH und R' = keine Gruppe, C₁-C₁₀-Alkyl oder Aryl, und R'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄, wobei Polymere gemäß der Formel:

worin x = 0,5-20%, y = 99,5-80%, und R = C₂-C₆ bevorzugt sind, und wobei Polymere gemäß der Formel:

worin x = 0,5-20%, y = 99,5-80% spezifische Beispiele sind.In another embodiment, the polymer having the side group may have at least one nitrogen to which the side group is attached. Examples of polymers having at least one nitrogen to which the side group is attached include, but are not limited to, a polymer according to the following formula:

where x = 0.1-100%, y = 99.9-0%, and R = no group, C ₁ -C ₁₀ -alkyl, aryl or -COX-R'-, wherein X = O or NH and R '= no group, C ₁ -C ₁₀ -alkyl or aryl, and R''= H, C ₁ -C ₃ -alkyl, aryl, Na, K or NH ₄ , wherein polymers according to the formula:

wherein x = 0.5-20%, y = 99.5-80%, and R = C ₂ -C _{6 are} preferred, and wherein polymers according to the formula:

where x = 0.5-20%, y = 99.5-80% specific examples.

worin P = H, C₁-C₃-Alkyl, CO₂R'', CONHR
R = C₁-C₁₀-Alkyl, Aryl
R' = H, C₁-C₃-Alkyl oder Aryl
X = O, NH oder NR
R'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄.In another embodiment, the polymer having a side group or end group thereon containing -Si (OR ") _{3 is} derived from an unsaturated polymerizable monomer containing the group -Si (OR") ₃ , where R "= H, C ₁ -C ₁₀ alkyl, aryl, Na, K or NH ₄ and optionally copolymerized with one or more additional polymerizable monomers. Examples of such additional polymerizable monomers include, but are not limited to, vinylpyrrolidone, (meth) acrylamide, N-substituted acrylamides such as N-alkylacrylamides or acrylamidomethylpropanesulfonic acid, (meth) acrylic acid and salts or esters thereof, maleimides, vinyl acetate, acrylonitrile and styrene. Particularly preferred unsaturated polymerizable monomers containing -Si (OR ") 3 groups are monomers of formulas V and VI.

wherein P = H, C ₁ -C ₃ alkyl, CO ₂ R ", CONHR
R = C ₁ -C ₁₀ -alkyl, aryl
R '= H, C ₁ -C ₃ alkyl or aryl
X = O, NH or NR
R "= H, C ₁ -C ₃ -alkyl, aryl, Na, K or NH ₄ .

worin P = H, R = -CH₂CH₂CH₂-, R' = H, X = NH, und R'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄.Examples of such polymers include homo- and copolymers of trialkoxyvinylsilanes such as CH ₂ = CHSi (OCH ₂ CH ₃ ) ₃ , and monomers of Formula VII: Formula VII:

wherein P = H, R = -CH ₂ CH ₂ CH ₂ -, R '= H, X = NH, and R "= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ .

monomers of this type with any other polymerizable monomers such as those listed above be copolymerized described. Particularly preferred copolymerizable Monomers include vinylpyrrolidone, (meth) acrylamide, N-substituted (Meth) acrylamides, (meth) acrylic acid and their salts or esters, and maleimides. Particularly preferred N-substituted acrylamides containing 4-20 carbon atoms, such as N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-amylacrylamide, N-hexylacrylamide, N-penylacrylamide, N-octylacrylamide.

verwendet, worin w = 0-99%, x = 1-99%, y = 1-99%, z = 0,5-20%, und M = H, Na, K, NH₄; und R'' = H, C₁-C₁₀-Alkyl, Aryl, Na, K oder NH₄; P = H oder CH₃; L = H oder C₁-C₁₀-Alkyl, Aryl oder Aralkyl; F = -G-R-X-R'-Si(OR'')₃, worin G = keine Gruppe, NH, NR'' oder O; R = keine Gruppe, C=O, O, C₁-C₁₀-Alkyl oder Aryl; X = keine Gruppe, NR, O, NH, Amid, Urethan oder Harnstoff; R' = keine Gruppe, O, C₁-C₁₀-Alkyl oder Aryl; und R'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄, und worin VPD ein Rest ist, der von einem substituierten oder unsubstituierten Vinylpyrrolidonmonomer abgeleitet ist. Beispiel derartiger Polymere sind Homo- oder Copolymere von einem oder mehreren Comonomeren der Formeln VII: Formel VII:

worin P = H, R = -CH₂CH₂CH₂-, R' = H, X = NH, und R'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄, wobei Polymere gemäß der nachfolgenden Formel:

worin w = 0-90%, x = 0-50%, y = 0-90%, z = 2-50 Mol-%, spezifische Beispiele sind.In a preferred embodiment, a polymer according to the formula:

where w = 0-99%, x = 1-99%, y = 1-99%, z = 0.5-20%, and M = H, Na, K, NH ₄ ; and R "= H, C ₁ -C ₁₀ alkyl, aryl, Na, K or NH ₄ ; P = H or CH ₃ ; L = H or C ₁ -C ₁₀ alkyl, aryl or aralkyl; F = -GRX-R'-Si (OR '') ₃ , where G = no group, NH, NR '' or O; R = no group, C = O, O, C ₁ -C ₁₀ -alkyl or aryl; X = no group, NR, O, NH, amide, urethane or urea; R '= no group, O, C ₁ -C ₁₀ -alkyl or aryl; and R "= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ , and wherein VPD is a radical derived from a substituted or unsubstituted vinylpyrrolidone monomer. Examples of such polymers are homopolymers or copolymers of one or more comonomers of the formula VII: embedded image

wherein P = H, R = -CH ₂ CH ₂ CH ₂ -, R '= H, X = NH, and R "= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ , wherein Polymers according to the following formula:

where w = 0-90%, x = 0-50%, y = 0-90%, z = 2-50 mole%, specific examples.

verwendet, worin w = 1-99,9%, x = 0,1-50%, y = 0-50%, z = 0-50%; und Q = C₁-C₁₀-Alkyl, Aryl, Amid, Acrylat, Ether, COXR, wobei X = O oder NH und R = H, Na, K, NH₄, C₁-C₁₀-Alkyl oder Aryl, oder ein beliebiger andere Substituent; X = NH, NP, worin P = C₁-C₃-Alkyl oder Aryl, oder O; R' = C₁-C₁₀-Alkyl oder Aryl; V'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄ oder einen Anhydridring bildet; R'' = H, C₁-C₃-Alkyl, Aryl, Na, K oder NH₄; und D = NR1₂ oder OR1, worin R1 = H, C₁-C₂₀-Alkyl, C₁-C₂₀-Alkenyl oder Aryl, mit der Maßgabe, dass alle R-, R''-, V''- und R1-Gruppen nicht gleich sein müssen, und wobei Polymere gemäß den Formeln:

worin w = 1-99,9%, x = 0,1-50%, y = 0-50%, z = 0-50%; und Q gleich Phenyl ist, und

worin w = 1-99,9%, x = 0,1-50%, y1 + y2 = 0-50%, y1 und y2 = 0-50%, z = 0-50%; und Q gleich Phenyl ist, spezifische Beispiele sind.In another embodiment, a polymer according to the formula

where w = 1-99.9%, x = 0.1-50%, y = 0-50%, z = 0-50%; and Q = C ₁ -C ₁₀ alkyl, aryl, amide, acrylate, ether, COXR, wherein X = O or NH and R = H, Na, K, NH ₄ , C ₁ -C ₁₀ alkyl or aryl, or any other substituent; X = NH, NP, wherein P = C ₁ -C ₃ alkyl or aryl, or O; R '= C ₁ -C ₁₀ alkyl or aryl; V "= H, C ₁ -C ₃ -Al kyl, aryl, Na, K or NH ₄ or an anhydride ring; R "= H, C ₁ -C ₃ -alkyl, aryl, Na, K or NH ₄ ; and D = NR 1 ₂ or OR ₁ , wherein R ₁ = H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkenyl or aryl, with the proviso that all R, R ", V", and R1 groups need not be the same, and polymers according to the formulas:

where w = 1-99.9%, x = 0.1-50%, y = 0-50%, z = 0-50%; and Q is phenyl, and

where w = 1-99.9%, x = 0.1-50%, y1 + y2 = 0-50%, y1 and y2 = 0-50%, z = 0-50%; and Q is phenyl, specific examples are.

In another embodiment, a polymer according to the formula AO- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y (CH ₂ CH ₂ O) _Z -OB where x = 5-100% (as mol%), y and z = 0-100%, and wherein at least one A unit and / or B unit is a group having the group -Si (OR '') ₃ , wherein R "= H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ . Examples of such polymers include AO- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y (CH ₂ CH ₂ O) _Z -OB, wherein A and / or B = R-Si (OR ''). ) ₃ , and x = 5-50%, y = 5-95%, and z = 0-50%, ie, a -Si (OR ") ₃ group-substituted copolymer of ethylene oxide and propylene oxide, and AO- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y (CH ₂ CH ₂ O) _z -OB, wherein A and / or B = R-Si (OR '') ₃ , and x = 100% , y = 0% and z = 0%, ie a -Si (OR ") ₃ group substituted homopolymer of polyethylene oxide is used.

In another embodiment, a polymer made from a polysaccharide or polysaccharide derivative is used. Any polysaccharide to which -Si (OR ") ₃ side groups can be attached can be used. Preferably, the polysaccharide should be soluble in the industrial process stream, such as the liquor from Kratfzellstoffmühle process streams or the process stream of high level nuclear waste. Polysaccharides useful in this invention include, but are not limited to, cellulose and its derivatives, such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxybutylcellulose, carboxymethylcellulose, starch, and starch derivatives, such as cationic starch, guar, dextran, dextrins, xanthan, Agar, carrageenan, and the like. Particularly preferred are starch and cellulose derivatives, wherein the reaction product of hydroxyethyl cellulose with 3-glycidooxypropyltrimethoxysilane is a specific example.

The polymers used in this invention can be prepared in a number of ways. For example, they can be prepared by polymerizing a group -Si (OR ") ₃ -containing monomer wherein R" = H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ such as, for example, a Silane monomer, or by copolymerizing such a monomer with one or more comonomers. Suitable silane monomers for use in the present invention include, but are not limited to, vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, gamma-N-acrylamidopropyltriethoxysilane, p-triethoxysilylstyrene, 2- (methyltrimethoxysilyl) acrylic acid, 2- (methyltrimethoxysilyl) -1,4- butadiene, N-Triethoxysilylpropylmaleimid and other reaction products of MaAleinsäureanhydrid and other unsaturated anhydrides with amino compounds containing the group -Si (OR '') ₃ . These monomers can be hydrolyzed either before or after the polymerization by an aqueous base. Suitable comonomers for use in the present invention include, but are not limited to, vinyl acetate, acrylonitrile, styrene, (meth) acrylic acid and its esters or salts, (meth) acrylamide and substituted acrylamides such as acrylamidomethylpropanesulfonic acid, N-methylacrylamide, N, N Dimethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-amylacrylamide, N-hexylacrylamide, N-phenylacrylamide, N-octylacrylamide. The copolymers may also be graft copolymers such as polyacrylic acid g-polyvinyl (triethoxysilane) and poly (vinyl acetate-co-crotonic acid) -g-poly (vinyltriethoxysilane). These Polymers can be made in a variety of solvents. Solvents suitable for such use include, but are not limited to, acetone, tetrahydrofuran, toluene, xylene, etc. In some instances, the polymer is soluble in the reaction solvent and is recovered by stripping off the solvent. Alternatively, if the polymer is not soluble in the reaction solvent, the product is recovered by filtration. Suitable initiators for use in the present invention include, but are not limited to, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2-azobisisobutyronitrile, benzoyl peroxide and cumene hydroperoxide.

In another embodiment of the present invention, polymers suitable for use in the invention can be prepared by containing a compound containing a -Si (OR ") ₃ group as well as a reactive group having either a pendant group or a backbone atom of an existing polymer is reacted. For example, polyamines and polysaccharides can be reacted with a variety of compounds containing -Si (OR ") ₃ groups to give polymers which can be used in the invention. Suitable reactive groups include, but are not limited to, an alkylhalogen group such as, for example, chloropropyl, bromoethyl, chloromethyl and bromoundecyl. The compound containing -Si (OR ") ₃ may contain an epoxy functionality such as glycidoxypropyl, 1,2-epoxyamyl, 1,2-epoxydecyl or 3,4-epoxycylohexylethyl. 3-glycidoxypropyltrimethoxysilane is a particularly preferred compound.

The reactive group may also be a combination of a hydroxyl group and a halogen, such as 3-chloro-2-hydroxypropyl. The reactive one The remainder may also contain an isocyanate group, such as isocyanatopropyl or isocyanatomethyl which form a urea linkage upon reaction. additionally are silanes containing anhydride groups, such as triethoxysilylpropylsuccinic anhydride for use in the preparation of the polymers for the present invention Invention suitable. The reactions can be either solvent-free or in a suitable solvent carried out become. additionally can other functional groups such as alkyl groups are added, by reacting other amino groups or nitrogen atoms on the polymer with alkyl halides, epoxides or isocyanates. The polyamines can be prepared by a number of methods. You can go through a ring-opening polymerization of aziridine or the like Connections are made. You can also by condensation reactions of amines such as ammonia, methylamine, dimethylamine, ethylenediamine etc. with reactive compounds such as 1,2-dichloroethane, epichlorohydrin, Epibromohydrin and the like Connections are made.

polymers which contain anhydride groups can with a series of -Si (OR '') 3-containing compounds be reacted to produce polymers which are for use in the present invention are suitable. Suitable anhydride-containing polymers include copolymers of maleic anhydride with ethylenically unsaturated Monomers such as styrene, ethylene, alpha-olefins such as octadecene, meth (acrylamide), (Meth) acrylic acid, Acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, Butyl acrylate and methyl vinyl ether. The polymer may also be a graft copolymer such as poly (1,4-butadiene) -g-maleic anhydride or polyethylene-g-maleic anhydride and the same. Other suitable anhydride monomers include but not limited on itaconic anhydride and citraconic anhydride. suitable reactive silane compounds include, but are not limited to, γ-aminopropyltriethoxysilane, bis (gamma-triethoxysilylpropyl) amine, N-phenyl-gamma-aminopropyltriethoxysilane, p-aminophenyltriethoxysilane, 3- (m-aminophenoxypropyl) trimethoxysilane, and gamma-aminobutyltriethoxylsilane. Other functional groups can added to the polymer Be prepared by adding amines, alcohols and other compounds is implemented. In a preferred polymer for use in the maleic anhydride is the anhydride and is the comonomer styrene. A preferred silane is gamma-aminopropyltriethoxysilane. It is also beneficial to have some of the anhydride groups with one another To implement amine such as diethylamine.

The same type of amine compound containing a -Si (OR ") ₃ group can be reacted with polymers containing an isocyanate side group, such as copolymers of, for example, isopropenyldimethylbenzyl isocyanate and vinyl isocyanate with comonomers, including, but not limited to, vinyl acetate, styrene , Acrylic acid and acylamide. These polymers can also be reacted with other compounds, such as amines, to enhance performance.

Isocyanate-functional compounds having a -Si (OR ") ₃ group, such as gamma-isocyanatopropyltrimethoxysilane, can also be reacted with polymers containing hydroxyl groups, such as hydrolyzed poly (vinyl acetate) and copolymers of vinyl acetate with other monomers. Other hydroxyl-containing polymers suitable for use include, but are not limited to, poly saccharides and polymers containing N-methylolacrylamide.

in the inventive method For example, the amount of polymer added to the process stream may be added of the composition of the relevant industrial process stream (e.g., liquor from process streams a kraft pulp mill or of high-grade nuclear waste), and everything in general is required, is an amount of which inhibits aluminum silicate-containing deposits. In general, the polymer is preferred in the process stream economically favorable and for the Practice cheap Concentrations added. A preferred concentration is one from more than about 0 ppm (parts per million) to about 300 ppm, stronger preferably, the polymer is the process stream in a concentration from more than 0 ppm to about 50 ppm, and most preferably in at a concentration greater than about 0 ppm to about 10 ppm.

The Polymer can go directly to any industrial process stream may be added, in which deposits may occur, e.g. the evaporation equipment of black liquor in kraft pulp process, and green liquor and white liquor process streams this Process. However, it is preferred to add the polymer to a feed stream or a recycle stream or add to brine leading to the black liquor evaporation apparatus. Although the polymer is the industrial process stream to any Time during of the process can be added, it is preferred to use it on a favorable point in the process, before or during Applied heat is going to admit. Usually the polymer is added immediately before the evaporation equipment.

severe nuclear waste

Comparative Example A

Preparation of the reaction product of a styrene / maleic anhydride copolymer with butylamine (Comparative Polymer A) is as follows: 10.0 g dry styrene / maleic anhydride copolymer (SMA), having a mole ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000 are suspended in 100 ml of toluene. A solution of 1.72 g of butylamine in 10 ml of toluene is added at ambient temperature. The mixture is refluxed for 3 hours. The solid product is filtered off, washed and dried. This results in a polymer containing 53 mole% styrene, 24 mole% N-butyl halide of maleic anhydride, and 23 mole% maleic anhydride.

Comparative example B

Preparation of the reaction product of SMA with tallow amine and diethyl amine (Comparative Polymer B) is as follows: 100.0 g dry SMA, with a mole ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000, are reported in 941.7 g of toluene suspended. A solution of 25.2 g of tallowamine and 27.5 g of diethylamine in 35.2 g of toluene is added at ambient temperature and then the mixture is heated at reflux for 30 minutes. The resulting toluene slurry is cooled to room temperature and then added with mixing to about 700 ml of 2% aqueous brine. The toluene phase is separated and the toluene residue in the aqueous phase is removed by distillation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyethersulfone filter and then freeze-dried to obtain the dry polymer. This yields a polymer containing 53 mole% styrene, 38 mole% N-diethyl-halide of maleic anhydride, and 9 mole% N-tallow hemiamide of maleic anhydride.

Comparative example C

The Preparation of a copolymer of N-tert-octylacrylamide and acrylic acid (Comparative Polymer C) is carried out as follows: 2.81 g of acrylic acid, 2.52 g of N-tert-octylacrylamide and 0.14 g of 2-mercaptoethanol are dissolved in 12.5 g of DMF and 13.87 g of dioxane disbanded and purged with nitrogen. The mixture is brought to 75.degree heated and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 3 g of dioxane are added. After 6 h at 75 ° C, the mixture is cooled, wherein the wished Polymer in solution is obtained. This gives a polymer containing 73.7 mol% of acrylic acid and 26.3 mol% N-tert-octylacrylamide.

Example 1 - Polymer I

Preparation of the reaction product of SMA with butylamine and (3-aminopropyl) triethoxysilane to give a polymer containing 1 mole% of silane-containing monomer units (Polymer I) is done as follows: 10.0 g dry SMA, with a molar ratio of Styrene to maleic anhydride of about 1.0 and an M _w of about 16,000 are suspended in 100 ml of toluene. A solution of 1.72 g of butylamine and 0.21 g of (3-aminopropyl) triethoxysilane in 10 ml of toluene is added at ambient temperature. The mixture is refluxed for 3 hours. The solid product is filtered off, washed and dried. This yields a polymer containing 53 mole% styrene, 23.9 mole% N-butyl-halide of maleic anhydride, 1 mole% of N- (3-triethoxysilyl) -propyl-half-amide of maleic anhydride and 22.1 mole% of maleic anhydride.

Example 2 - Polymer II

Preparation of the reaction product of SMA with butylamine and (3-aminopropyl) triethoxysilane to give a polymer having 3.8 mole% silane-containing monomer units (Polymer II) is done as follows: 10.0 g dry SMA, with a Molar ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000, are suspended in 100 ml of toluene. A solution of 1.72 g of butylamine and 0.83 g of (3-aminopropyl) triethoxysilane in 10 ml of toluene is added at ambient temperature. The mixture is refluxed for 3 hours. The solid product is filtered off, washed and dried. This gives a polymer containing 53 mole% styrene, 23.9 mole% N-butyl-halide of maleic anhydride, 3.8 mole% of N- (3-triethoxysilyl) -propyl-halamide of maleic anhydride and 19.3 mole% of maleic anhydride.

Example 3 - Polymer III

Preparation of the reaction product of SMA with butylamine and (3-aminopropyl) triethoxysilane to give a polymer having 7.6 mole% silane-containing monomer units (Polymer III) is done as follows: 10.0 g dry SMA, with a Molar ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000, are suspended in 100 ml of toluene. A solution of 1.72 g of butylamine and 1.66 g of (3-aminopropyl) triethoxysilane in 10 ml of toluene is added at ambient temperature. The mixture is refluxed for 3 hours. The solid product is filtered off, washed and dried. This gives a polymer containing 53 mole% styrene, 23.9 mole% N-butyl-halide of maleic anhydride, 7.6 mole% of N- (3-triethoxysilyl) -propyl-half-amide of maleic anhydride and 15.5 mole% of maleic anhydride.

Example 4 - Polymer IV

Preparation of the reaction product of SMA with tallowamine, diethylamine and (3-aminopropyl) triethoxysilane to give a polymer having 3.8 mole% silane-containing monomer units (Polymer IV) is as follows: 100.0 g dry SMA, with a molar ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000 are suspended in 941.7 g of toluene. A solution of 25.2 g of tallowamine, 24.8 g of diethylamine and 8.3 g of (3-aminopropyl) triethoxysilane in 38.9 g of toluene is added at ambient temperature and then the mixture is heated at reflux for 30 minutes. The resulting toluene slurry is cooled to room temperature and then added with mixing to about 700 ml of 2% aqueous brine. The toluene phase is separated and the toluene residue in the aqueous phase is removed by distillation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyethersulfone filter and then freeze-dried to obtain the dry polymer. This yields a polymer containing 53 mole% styrene, 3.8 mole% N- (3-triethoxysilyl) propyl-halide of maleic anhydride, 9.4 mole% N-tallow hemiamide of maleic anhydride and 33.8 mole% N, N -Diethylhalbamid from maleic anhydride.

Example 5 - Polymer V

Preparation of the reaction product of SMA with tallowamine, diethylamine and (3-aminopropyl) triethoxysilane to give a polymer having 7.5 mole% silane-containing monomer units (Polymer V) is as follows: 100.0 g dry SMA, with a molar ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000 are suspended in 941.7 g of toluene. A solution of 20.2 g of tallowamine, 23.4 g of diethylamine and 16.7 g of (3-aminopropyl) triethoxysilane in 40.2 g of toluene is added at ambient temperature and then the mixture is heated at reflux for 30 minutes. The resulting toluene slurry is cooled to room temperature and then added with mixing to about 700 ml of 2% aqueous brine. The toluene phase is separated and the toluene residue in the aqueous phase is removed by distillation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyethersulfone filter, and then freeze-dried to obtain the dry polymer. This gives a polymer containing 53 mole% styrene, 7.5 mole% N- (3-triethoxysilyl) propyl-halide of maleic anhydride, 7.5 mole% of N-tallow hemiamide of maleic anhydride and 30 mole% of N, N-diethyl-halide from maleic anhydride.

Example 6 - Polymer VI

Preparation of the reaction product of SMA with tallowamine, diethylamine and (3-aminopropyl) triethoxysilane to give a polymer having 3.8 mole% silane-containing monomer units (Polymer VI) is as follows: 100.0 g dry SMA, with a molar ratio of styrene to maleic anhydride of about 1.1 and an M _w of about 16,000 are suspended in 941.7 g of toluene. A solution of 10.1 g of tallowamine, 28.9 g of diethylamine and 8.3 g of (3-aminopropyl) triethoxysilane in 31.3 g of toluene is added at ambient temperature and then the mixture is heated at reflux for 30 minutes. The resulting toluene slurry is cooled to room temperature and then added with mixing to about 700 ml of 2% aqueous brine. The toluene phase is separated and the toluene residue in the aqueous phase is removed by distillation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyethersulfone filter and then freeze-dried to obtain the dry polymer. This yields a polymer containing 53 mole% styrene, 3.8 mole% N- (3-triethoxysilyl) propyl-halide of maleic anhydride, 3.8 mole% N-tallow hemiamide of maleic anhydride and 39.4 mole% N, N -Diethylhalbamid from maleic anhydride.

Example 7

The Production of n- (3-triethoxysilyl) propylacrylamide (TESPA) happens as follows: 197.4 g of (3-aminopropyl) triethoxysilane and 89.9 g of triethylamine are dissolved in 330 g of THF, purged with nitrogen, and at 0 ° C cooled. With mixing 83.9 g of acryloyl chloride are added dropwise, and after the mixture is heated at 40 ° C for 2 h. The mixture is at room temperature chilled and the salt filtered off. The resulting TESPA solution (42%) in THF) is used as is without further purification.

Example 8 - Polymer VII

The Preparation of the Tetra Polymer from N-tert-octylacrylamide, acrylic acid, 1-vinyl-2-pyrrolidinone and TESPA, a polymer containing 5 mol% of silane-containing monomer units (Polymer VII) is as follows: 1.89 g of 1-vinyl-2-pyrrolidinone, 0.66 g acrylic acid, 2.21 g of N-tert-octylacrylamide, 1.30 g of TESPA (42% in THF) and 0.14 g of 2-mercaptoethanol are dissolved in 14 g of DMF and 11.64 g of dioxane and washed with Flushed with nitrogen. The mixture is brought to 75.degree heated and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 3 g of dioxane are added. After 6 h at 75 ° C, the mixture is cooled, wherein the wished Polymer in solution is obtained. The polymer is made by precipitation with isopropyl alcohol further cleaned, washed and dried. This gives a polymer, containing 42.5 mol% 1-vinyl-2-pyrrolidinone, 22.5 mol% acrylic acid, 5 mol% TESPA and 30 mol% N-tert-octylacrylamide.

Example 9 - Polymer VIII

The Preparation of the copolymer of 1-vinyl-2-pyrrolidinone and TESPA, a polymer containing 5 mol% of silane-containing monomer units (Polymer VIII) is done as follows: 4.69 g of 1-vinyl-2-pyrrolidinone, 1.44 g of TESPA (42% in THF) and 0.14 g of 2-mercaptoethanol are dissolved in Dissolved 12.5 g of DMF and 13.07 g of dioxane and purged with nitrogen. The Mixture is at 75 ° C heated and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 3 g of dioxane are added. After 6 h at 75 ° C, the mixture is cooled, wherein the wished Polymer in solution obtained at 15% concentration. This gives a polymer containing 95 mole% 1-vinyl-2-pyrrolidinone and 5 mol% TESPA.

Example 10 - Polymer IX

The Preparation of the terpolymer of N-tert-octylacrylamide, acrylic acid and TESPA, a polymer containing 5 mole% of silane-containing monomer units (Polymer IX) is done as follows: 2.46 g of acrylic acid, 2.21 g N-tert-octylacrylamide, 1.56 g TESPA (42% in THF) and 0.14 g 2-mercaptoethanol are dissolved in 12.5 g of DMF and 12.97 g of dioxane and purged with nitrogen. The Mixture is at 75 ° C heated and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 3 g of dioxane are added. After 6 h at 75 ° C, the mixture is cooled, wherein the wished Polymer in solution obtained at 15% concentration. This gives a polymer containing 70 mol% acrylic acid, 5 mol% TESPA and 25 mol% N-tert-octylacrylamide.

Example 11 - Polymer X

The preparation of the reaction product of polyethylene oxide with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 2.2 mole% of silane-containing monomer units (polymer X) is as follows: 20.0 g of polyethylene oxide (M _n about 2,000) are prepared in Dissolved 10.0 g of DMSO and purged with nitrogen. To this mixture is added 2.63 g of 3-glycidoxypropyltrimethoxysilane, followed by 1.36 g of 45% KOH. The resulting mixture is heated to 80 ° C for 1 h to give the desired polymer in solution at 65.8% concentration. This yields a polymer containing about 97.8 mole% ethylene oxide and 2.2 mole% 3-glycidoxypropyltrimethoxysilane.

Example 12 - Polymer XI

Preparation of the reaction product of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 3.1 mole percent silane-containing monomer units (polymer XI). is done as follows: 30.0 g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (with 50% by weight of ethylene oxide and a M _n of about 1,900) under nitrogen with 4.52 g 3-glycidoxypropyltrimethoxysilane mixed. 2.34 g of 45% KOH are added and the resulting mixture is heated to 80 ° C for 1 h to give the desired polymer at 92.6% concentration. This yields a polymer containing about 55.1 mole percent ethylene oxide, 41.8 mole percent propylene oxide, and 3.1 mole percent 3-glycidoxypropyltrimethoxysilane.

Example 13 - Polymer XII

Preparation of the reaction product of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 3.0 mole% silane-containing monomer units (polymer XII). is as follows: 30.0 g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (with 10 wt .-% ethylene oxide and an M _n of about 2000) is charged under nitrogen with 4.3 g 3-glycidoxypropyltrimethoxysilane mixed. 2.22 g of 45% KOH are added and the resulting mixture is heated to 80 ° C for 1 h to yield the desired 92.9% concentration polymer. This yields a polymer containing about 12.3 mole percent ethylene oxide, 84.7 mole percent propylene oxide, and 3.0 mole percent 3-glycidoxypropyltrimethoxysilane.

Example 14 - Polymer XIII

The preparation of the reaction product of polyethylenimine with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 0.5 mole% of silane-containing monomer units (polymer XIII) is as follows: 25.4 g of polyethylenimine ( _Mw about 25,000) are added 0.7 g of 3-glycidoxypropyltrimethoxysilane is mixed, and the resulting mixture is heated at 70 ° C for 16 hours to give the desired polymer as a soft, fragile gel.

Example 15 - Polymer XIV

Preparation of the reaction product of polyethylenimine with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 1.0 mole percent of silane-containing monomer units (Polymer XIV) is as follows: 25.72 grams of polyethyleneimine ( _Mw about 25,000) are added 1.43 g of 3-glycidoxypropyltrimethoxysilane are mixed, and the resulting mixture is heated at 70 ° C for 16 hours to give the desired polymer as a soft, fragile gel.

Example 16 - Polymer XV

The preparation of the reaction product of polyethylenimine with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 2.0 mole% of silane-containing monomer units (Polymer XV) is as follows: 11.39 g of polyethyleneimine ( _Mw about 25,000) are added 1.28 g of 3-glycidoxypropyltrimethoxysilane are mixed, and the resulting mixture is heated at 70 ° C for 16 hours to give the desired polymer as a soft, fragile gel.

Example 17 - Polymer XVI

The production of the reaction product of polyethylenimine with 3-glycidoxypropyltrimethoxysilane to give a polymer containing 4.0 mol% of silane-containing monomer units (Polymer XVI) is done as follows: 10.0 g of polyethylene imine _(Mw 25,000) are mixed with 2.29 g of 3-glycidoxypropyltrimethoxysilane, and the resulting mixture is heated 16 h at 70 ° C, giving the desired polymer is obtained as a soft, fragile gel ,

Example 18 - Polymer XVII

• * Mol-% von Monomereinheiten in dem Polymer, enthaltend die Silan-funktionelle Gruppe

Preparation of the reaction product of hydroxyethylcellulose with 3-glycidoxypropyltrimethoxysilane to give a polymer containing a high proportion (~ 30 mol%) of silane-containing monomer units (Polymer XVII) is as follows: 8.0 g of dry hydroxyethylcellulose (molecular weight 24,000 to 27,000) are mixed with 2.0 g of 3-glycidoxypropyltrimethoxysilane in 5 g of acetone. The acetone is removed by evaporation and the resulting mixture is heated at 100 ° C for 16 h to give the desired polymer. Table 1 Summary of the polymers used in the deposit inhibition tests

• * Mol% of monomer units in the polymer containing the silane functional group

Example 19

test method

A synthetic high grade nuclear waste liquor is manufactured by Addition of sodium carbonate, sodium sulfate, sodium hydroxide, sodium aluminate solution (prepared by digesting alumina trihydrate in brine), sodium silicate, Sodium nitrate and sodium nitrite to deionized water. The final composition the liquor is shown in Table 2.

Table 2

In front Adding to the nuclear waste liquor all polymer samples in 2% aqueous NaOH dissolved to all anhydride groups and trialkoxysilane groups not previously have hydrolyzed, the trialkoxysilane groups be converted into silanol groups or the sodium salts. The deposit reducing Additive (if used) is placed in a 125 ml polyethylene bottle given as a 0.5% solution in 2% aqueous NaOH for the lower dosages, and for the higher dosages becomes one 3% solution used. 120 ml of the above synthetic high-grade nuclear waste stock solution then added to the bottle with mixing. The locked Bottle becomes 18 ± 2 Hours under motion at 102 ° C heated. Up to 24 such tests (bottles) are carried out simultaneously. At the At the end of the 18 hours the bottles are opened and the solution becomes filtered (0.45 microns Filter). It is observed that considerable aluminum silicate deposits form as a loose aluminum silicate in the liquor (which is initially on the polyethylene surfaces may have formed). In the examples below, the weight of the test Deposit expressed as a percentage of the mean weight of deposits, in two comparative blank tests (i.e., without use of additive) which are part of the same test batch were.

Under Using the test method given above become a Series of butylamine reacted SMA polymers which vary Amounts of silane contain an activity to inhibit aluminum silicate deposits examined and the results are given in Table 3.

Table 3

Example 20

Under Use of the test procedure given in Example 19 a series of tallow amine and diethyl amine reacted SMA polymers, which contain varying amounts of silane, an activity for inhibition examined by deposits, and the results are in table 4 indicated.

Table 4

Example 21

Under Use of the test procedure given in Example 19 a series of polymers containing the silane-containing monomer TESPA were prepared for an activity to inhibit deposits examined and the results are given in Table 5.

Table 5

Example 22

Under Use of the test procedure given in Example 19 a series of polyether-type polymers containing varying amounts on silane, on an activity to inhibit deposits examined and the results are given in Table 6.

Table 6

Example 23

Under Use of the test procedure given in Example 19 a series of polyethyleneimine-type polymers which vary Contains quantities of silane, on an activity for the inhibition of deposits examined and the results are given in Table 7.

Table 7

Example 24

Under Use of the test procedure given in Example 19 becomes Hydroxyethylcellulosederivat containing silane, an activity for inhibition examined by deposits, and the results are in table 8 indicated.

Table 8

Test for inhibition of Deposits in a kraft pulp mill

Example 25

Around to simulate the conditions that exist in a typical black liquor encountered a kraft pulp mill becomes a synthetic process liquor, which is a typical Black liquor simulated, prepared in the following way.

A basic aluminate solution according to the following formula is prepared by adding the aluminum min and the NaOH solution are added to the water and stirred overnight. The solution is then filtered through a 3 μm filter membrane (Pall Versapor-3000 T w / wa, 47 mm): Na ₂ O.Al ₂ O ₃ .3H ₂ O 100.0 g 50% NaOH 146.6 g Deionized water 753.4 g total 1000.0 g

This basic aluminate solution is used to prepare a solution simulating a kraft black liquor according to the recipe given below and the procedure given below. Sodium acetate is added to achieve the desired concentration of sodium ions. Quantities are in grams and percentages are in w / w (w / w) unless otherwise specified. sodium 121.9 sodium sulphate 32.7 sodium thiosulfate 36.4 Sodium hydrosulfide, 60% 70.9 sodium 445.3 50% sodium hydroxide 290.7 29.55% SiO ₂ 14.0 Basic aluminate solution 25.1 Deionized water 1746 total 2783 g = 2.30 liters Calculated concentration: [CO ₃ ^2- ] = 0.5M [SO ₄ ^2- ] = 0.1M [S ₂ O ₃ ^2- ] = 0.1M [SH ^- ] = 0.33 M [Na ⁺ ] = 5.7 m [OH ^- ] = 1.6M [Si] = 0.03 M [Al] = 0.01M

The solution is prepared by the sodium carbonate, sodium sulfate, sodium thiosulfate, Sodium hydrosulfide and sodium acetate under vigorous stirring be added to the water. After stirring for 30 minutes, the solution is passed through a coarse glass frit filtered to small amounts of insoluble Remove material.

The sodium hydroxide, Siliziumoxidlösung and finally the basic aluminate solution are added with stirring after each addition. The solution is used immediately as described below.

For each of Examples 26 to 33, the respective polymer solutions of Polymers III (Example 3), V (Example 5), VII (Example 8), VIII (Example 9), X (Example 11), XI (Example 12), XVI (Example 17) and XVII (Example 18) before use in 2% NaOH solution prediluted a 1% (w / w) active concentration.

The Amount of 1.45 g of a polymer solution (or 1.45 g of water for the control test) is added to a 4 ounce HDPE wide neck area. Thereafter, 145 g (120 ml) of kraft black liquor simulation solution are added each bottle added before they are closed and shaken. Each bottle then contained a "test solution". The polymer dose is 100 ppm.

The closures on the bottles are then loosened so that pressure can escape, and the bottles are placed on the bottom of a 102 ° C oven to simulate the heating of liquor in a force process. After 1.5 hours, the closures are tightened and the bottles are placed on a turntable placed in the oven. After setting the turntable in the oven overnight (16.5 h), each sample is filtered using a weighed 3 μm filter membrane (Pall Versapor-3000 T w / wa, 47 mm). Each membrane plus all of the collected solid is washed with about 5 mL of water and placed on a 2.5 inch glass jar. A steel tray containing all the watch glasses and membranes is placed in a 102 ° C oven for 30 minutes to dry the filtered solids. Each membrane plus solid is weighed and the weight of the solid calculated by subtraction. % Inhibition of deposits is then calculated in the following way:

The Results of polymer tests in Examples 26-33 at 100 ppm are shown in Table 9.

Table 9

Claims (15)

A composition for use in reducing aluminosilicate deposits in an alkaline industrial process comprising a polymer of the formula:

where w = 1-99.9%, x = 0.1-50%, y = 0-50%, z = 0-50%; and Q = C ₁ -C ₁₀ alkyl, aryl, amide, acrylate, ether, COXR, wherein X = O or NH and R = H, Na, K, NH ₄ , C ₁ -C ₁₀ alkyl or aryl, or any other substituent; X = NH, NP, wherein P = C ₁ -C ₃ alkyl or aryl, or O; R '= C ₁ -C ₁₀ alkyl or aryl; V '' = H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ or an anhydride ring; R "= H, C ₁ -C ₃ -alkyl, aryl, Na, K or NH ₄ ; and D = NR 1 ₂ or OR ₁ , wherein R ₁ = H, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkenyl or aryl, with the proviso that all R, R ", V", and R1 groups do not have to be the same. A composition according to claim 1 comprising a polymer selected from the formula

where w = 1-99.9%, x = 0.1-50%, y = 0-50%, z = 0-50%; and Q is phenyl, and the formula

where w = 1-99.9%, x = 0.1-50%, y1 + y2 = 0-50%, y1 and y2 = 0-50%, z = 0-50%; and Q is phenyl. A composition for use in reducing aluminosilicate deposits in an alkaline industrial process comprising a polymer which is a polysaccharide having a side group or end group thereon containing formula I: -Si (OR '') ₃ Formula I wherein R "= Na, K or NH ₄ . A composition according to claim 3, wherein the polysaccharide a hydroxyethyl cellulose derivative. A composition according to claim 4, wherein the polysaccharide is a hydroxyethyl cellulose derivative and with 3-glycidoxypropyltrimethoxysilane implemented. A composition for reducing aluminum silicate deposits in an industrial process comprising a polymer which is a homopolymer or a copolymer derived from an unsaturated monomer of the formula V: Formula V:

wherein P = H, C ₁ -C ₃ alkyl, CO ₂ R ", CONHR R = C ₁ -C ₁₀ alkyl, aryl R '= H, C ₁ -C ₃ alkyl or aryl X = O, NH or NR R '' = H, C ₁ -C ₃ alkyl, aryl, Na, K or NH ₄ . A composition according to claim 6 comprising a polymer which is derived from monomers of the formula V and one or a plurality of polymerizable monomers selected from the group consisting of vinylpyrrolidone, (meth) acrylamide, N-substituted acrylamides, (Meth) acrylic acid and salts or esters thereof, and maleimides. A composition for reducing aluminum silicate deposits in an industrial process comprising a homopolymer or copolymer derived from monomers of formula VI: Formula VI:

wherein P = H, C ₁ -C ₃ alkyl, CO ₂ R ", CONHR R = C ₁ -C ₁₀ alkyl, aryl R '= H, C ₁ -C ₃ alkyl or aryl R" = Na , K or NH ₄ . A composition according to claim 8 comprising a polymer derived from monomers of formula VI and one or more polymerizable monomers selected from the group consisting of vinylpyrrolidone, (meth) acrylamide, N-substituted acrylamides, (meth) acrylic acid and salts or Esters thereof, and maleimides. A composition according to claim 6 or 8, wherein said Polymer is a copolymer of one or more comonomers of the formulas V or VI and one or more comonomers selected from the group consisting of vinylpyrrolidone, N-octylacrylamide, acrylic acid and Salting it is. A composition for reducing aluminosilicate deposits in an industrial process comprising a polymer of Formula XI: AO- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y (CH ₂ CH ₂ O) _z -OB Formula XI where x = 5-100%, y and z = 0-100%, and wherein at least one A unit and / or B unit is a group containing the group -Si (OR '') ₃ , where R ''= Na, K or NH ₄ . A composition according to claim 11, wherein x = 100%, y and z = 0% are used. A composition according to claim 11, wherein x = 5-50%, y = 5-95% and z = 0-50% be used. Composition for reducing aluminum silicate deposits in an industrial process comprising a polymer which the reaction product of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) with 3-glycidoxypropyltrimethoxysilane. Composition for reducing aluminum silicate deposits in an industrial process comprising a polymer which the reaction product of polyethylenimine with 3-glycidoxypropyltrimethoxysilane is.